Sulfurized additives for lubricating compositions



Patented Oct. 7, 1952 ,SUDEURIZEDCADDITIVES FOR LUBRICATING- COMPOSITIONS ,Abrali'a nD. .Kirshenhaum, Union, and' James M.

Boyle, Bayonne, N; J., assignors: to Standard Oil Development E'ompann a corporation of;

Delaware No Dra ng.

.AHnIication Avast 119G9 2.

Serial No. 111,343

r 19 Claims.

The present inventionmelatesto improvements in sulfurized additives for lubricating, compositions, to a method otpreparingsuch additives and to compositions containing them. 'In particular, the invention relates -to' additive compo sitionsprepared by treating monocyclic terpenio hydrocarbons and related materials 'liavinga' s-i-milar-unsaturated Snon-ammatic ringstructure, to incorporate sulfur, phosphorus and; chlorine-"or other halogen therein; thereby convert such 10 compositions intdextremepressure agents or oxidation or corrosion inhibitors for'lubricating oils and g ieafifist As is well known in theart, ordinary hydrocarbon oils, e. g., lubricatingoils' derivedfirom pe troleum, are good lubricants iorfimanypurposesi but are deficient in strength 0f'lub1i'cating"fi m' when subjectedatoahighunit pressures.v The same iss-tr-uexof .the synthetic oils, .i: e, estersgoihihasio:

antifrictionzabearings, gearing; and other mechanical'; spartsitsubjected toahighs. unit: pressuresylthez. untreatedaiubricatingz .oils: and; greases prepared; therefrom; areirequentlyb inadequate; toeprevent; metaletu-metal contact; and. consequently. injury tOl metal: surfaces; In. the lubrication of parts.v which aressubjectedibothtolextremelwhigh pres-.-- suresiandwm slidingzfriction; the needfon a film-=- strengthening or; oillerepl'acingi. lubricating Maddi tiver becomes: particularly: imperative. A; well" lmownexampleaisthe lubrication .of "hypoid :gears incautom'otive'. vehicles... Unit. pressures on contacting; elements ofs such gears --s0metimes attain the magnitude momentarily of a hundred thousand poundsper'square inch or more. Such gears, moreover, are subject tosliding contact as well as, -or as" distinguished trom, true-rolling contact,--and; hen'ce, they are particularly sub-- Jectttosevere and intolerable wearunless pro-- tected by an adequate-lubricant.

Numerous suggestions--have been made=-in= the prionartior. using-schlorinated, suliurized, and/or phosphorized products aslsuchnextreme pressure additives to mineral-base; and other oily lubri ca'nts;v ltii'awell. known that certain chlorinated products, a. gs chlorinated hydrocarbons, are capable: offv providing: a protective. film of metal" chlor-ide, apparently a mono-molecular film, by reacting-momentarilywith-metal el'ementssuch as gears which come -intocontact--under heavyunit loads and underconditions-giving risetoinstantaneous high temperatures over limited-Z areas. Likewise, certain prior art compositionsoontaining sulfur or phosphorus; 1 orboth, orcontaming chlorine or other halogen with-either: sul

- towards metals.

fur or phosphorus, or both; have .beenzsuggested';

as having good load-bearing; severe operating: conditions;v

prior art compounds. have been prepared on the theory that the halogen, and/or sulfur, and/or phQs h rus-.. rea ts with t e m t i s lf a ms.tanw e tmmely hin upp edly mono-male lecular) but adequately protective.film thereon properties under 0 preventseizure and. am ge o. the contac m ta e emen s be g :l-ubricated u th normaloil film, disruptedbythe; heavy impact, can be.- e s ab ishe s eoiisuch m teri ls h m e n. ccepte commercial by t e indu y. some othershave not been commercially successful; because of their. ,cost.. or .hecause of operating dee ficieneies u de ext eme yseve e 1 ndi i ns- The :me ent inv nt on i based. ne e: dis-r ov rt tha e r lat v l mexn ns a nd ieh1y -.erre tiv -,e reme pre sur dit ve ay: en n ed it-fir tttea nae mo qc i te r e e. h a l m n na pe ten t rDi Qlinamma terpinene, and the like, with a sulfur chloridend t en w th i whose.. s u su fide o nc rpoat all 1 h e r ell elit lfu c l rin and phase.

ph rusnto th 1 11 3 210 n uct T ese te rneneshave: the rnicaliormu as While any of the sulfu'r"chlorides maybe-used= to treat the terpenes, the monochl'oride S2C12-i$ preferred; For-thepho sphorussulfide;the'sesquisulfide P ss is preferredbecause-it tends toadd more phosphorus and less sulfur and; thereby to reduce the corrosivity-oi the reaction product Where this consideration isnot of too great. importance, the other phosphorus sulfides P285, etc, may be used in lieu of P483.

According to the present. invention, an -inex-- pensive lubricating oil additive is prepared pref erably by first partially reacting the monocyolic' In general, these.

terpene (diolefin), e. g., dipentene, with sulfur chloride and thereafter reacting the resulting product with the phosphorus sulfide. The sulfur chloride is preferably added in such quantities and reacted under such conditions that approximately one of the double bonds of the terpene, on the average, is saturated thereby. The phosphorus sulfide is then introduced and it reacts largely with the second double bond giving a single compound containing all three of the elements, phosphorus, sulfur and chlorine. The quantity of phosphorus sulfide used, however, is considerably less than that required to saturate the second double bond of all the terpene molecules. Apparently, some polymerization takes place. In general, only a small amount of phosphorus sulfide is used where the product is intended as an extreme pressure additive. Larger proportions may be used where the product is to be used in very small quantities as an oxidation or corrosion inhibitor.

The invention will be more fully understood by reference to the following specific examples.

Example I 797 g. (475 c. c.) of sulfur monochloride was added to 1 liter (841 g.) of special commercial dipentene (from Hercules Powder Co.). This special dipentene had the following composition: 6% a-pinene, 7% a-terpineol, 10% para cymene. 31% dipentene, 39% terpinolene, 132.4(8) para menthadiene, 2% residue. The para cymene appears to be the only non-reactive component. Therefore, only about 90% of the special dipentene takes partin the reaction. The sulfur monochloride was introduced into the terpene at a rate of 15-20 0. e. per minute at 75-100 C. with constant stirring. After all the S2012 was added, the product was heated at 75-100 C. for to 1 hour. The SzClz-treated "dipentene (mixture) gave an analysis of 17.4% chlorine and 23.7% sulfur.

150 g. of the S2Cl2-treated dipentene" was diluted with 150 g. of a naphthenic lube distillate of grade SAE 30. g. of P483 was added and heated with stirring for one hour at '125-150 C. HCl was liberated. After one hour of heating, there were added 25 g. Lorol B alcohol, which is a well known commercial mixture of C10 to C18 primary alcoholsypredominantly about C12, prepared from coconut oil, and heating was continued for minutes more. The product was blown with nitrogen gas and filtered through a commercial filter aid known as Hyfio. The final product contained 3.74% chlorine 13.65% sulfur 1.68% phosphorus The following blend of the above product was made:

This blend gave the following results:

Timken machine test: Pass 33 lbs. SAE machine test: Pass 300+ Copper strip test: Pass Example 11 150 g. (1.45 mols) of $012 was added dropwise (2.5 g./min.) to 210 g. (1.55 mols) of special dipentene (Hercules) with constant agitation. The temperature was kept between 40 and 60 C. by means of a water and ice bath. After all the 5012 was added, the product was first kept for A hour at about 20 C. and then for one hour at 75 to C. 300 g. of mineral base oil of 55 S. S. U. viscosity at 210 F. and 20 g. of P48: were then added and the mixture was heated for one hour at 150 C. Then 50 g. of Lorol B alcohol were added and heated at 125-150 C. for 4 hour more. The product was blown with nitrogen gas to remove HCl and H28 and light ends, and filtered through Hyfio."

The product had the following analysis:

4.08% chlorine 9.08% sulfur 1.82% phosphorus The following blend was made and tested for extreme pressure properties:

2.5 weight per cent of product 7.5 weight per cent chlorinated wax (40 weight per cent chlorine) I 90.0 weight per cent of a mixture of a steam refined Pennsylvania cylinder oil having a viscosity of 220 S. S. U. at 210 F. and a Mid- Continent acid refined oil having a viscosity of 50 S. S. U. at 210 F.

The blend gave the following results:

Timken'machine test: Pass 33 lbs. SAE machine test: Pass 280 lbs. Copper strip test: Pass case of the dichloride S012, the mol ratio of SCI:

to terpene may be 1/1 or as high as 2/1. The reaction temperature when employing S2Cl2 can be between 60 and 125 C., preferably from 75 to 100 C. When the dichloride is employed, it should be added at a lower temperature, such as 30 to 60 C. to avoid a violent reaction, and thereafter the reaction can be completed at a higher temperature such as 75 to 100 or 125 C. The addition reaction is substantially complete in from to 1 /2 or 2 hours. The phosphorus sulfide is then added, preferably in an amount which will give a product containing from about 0.04 to about 4.0 weight per cent of phosphorus on the 100% undiluted basis. This range corresponds to reacting from about 0.000875 to about 0.0875 mols P483 (containing 0.0035 to 0.35 atoms of phosphorus) per mol of S2Cl2-treated terpene. The reaction is conducted at a temperature of 100 to 175 C., preferably from 125 to C., until the reaction is substantially completed, requiring a time of from about A; to 2 hours. In general, the molar proportions of phosphorus sulfide will runbetween about 0.001 and 0.1.

The finished lubricantpreferably contains '2 quantity of a conventional chlorinated hydro-N long chain aliphatic structure;Thehalogenated hydrocarbon is, combined with a smaller quantity of thedipentene orother treated terpene.

A preferred composition range is from aboutv 80- 95%. of the, oil or other lubricant, 4 to 15% ofthemalogenated hydrocarbon; and 1 to of the: treated 'jterpene. Specifically, the preferred proportionsare about 90% of;the:lubricant, preferably mineral lubricating oil, with about 7.5% of the halogenated hydrocarbon and about 2.5% of the treated terpene.

In many cases, it is not necessary to use an auxiliary additive, such as the chlorinated hydrocarbon referred to above. Where extreme pressure requirements are not excessive, the terpene treated first with a sulfur chloride and subsequently with a phosphorus sulfide is quite adequate by itself. When the single additive is used, it preferably comprises from 2 to 20% of the weight of the total composition. More specifically, proportions of about 5 to 12% will ordinarily be used.

The present invention comprehends both the treated dipentene as a new product per se together with process for its treatment, and also the lubricating composition containing the treated dipentene or other terpene as an additive.

Lubricating compositions containing such addi-= tive may be of mineral or synthetic oil base, or both. They may also contain other conventional materials such as antioxidants, viscosity index improvers, thickeners, tackiness agents, pour point depressors, and the like. The additive itself may be used in straight mineral oils or in blends with synthetic oils and also in lubricating greases and lubricating compositions of widely varying consistencies.

While the treatment with sulfur chlorides and phosphorus sulfides has been described with par ticular reference to terpenes such as dipentene, it is applicable in general to hydrocarbons, and esters, acids, alcohol and ketonic derivatives thereof having the general unsaturated nonaromatic structure pointed out above. Thus it may be applied to abietic acid and lower alkyl esters thereof, such as Abalyn (methyl-abletate), Hercolyn (hydrogenated abletic esters), and the like.

What is claimed is:

1. An extreme pressure additive composition for lubricants consisting essentially of the reaction product or about 1 molar proportion of a monocyclic terpene with about 1 to 2 molar proportions of a sulfur chloride, the quantity of said sulfur chloride being substantially sufficient to saturate one double bond in said terpene, said reaction product being further reacted with about 0.001 to 0.1 molar proportion of phosphorus sulfide at a temperature of 100 to 175 C.

2. Composition according to claim 1 wherein the sulfur chloride is S2012.

3. Composition according to claim 1 wherein the sulfur chloride is SO12.

4. A lubricating composition consisting essentially of 80 to 95% by weight of mineral base lubricating oil, 1 to 5% of the reaction product of one molar proportion of a monocyclic terpene treated first with about 1 to 2 molar proportions of a sulfur chloride and reacted thereafter with about 0.001 to about 0.1 molar proportions of a phosphorus sulfide at a temperature of 100 to 175 C., and 4 to 15% of a halogenated long chain aliphatic. hydrocarbon; said sulfur chloride being. effective to. substantially 's'aturate an average/of about. one: double bond per terpene molecule'. and said phosphorussulfide being effective:

to. partially saturate, on the average,. the: second double bond of the terpenemolecule. 1

5;. A1 lubricating composition according. to. claim 4 wherein the sulfur chloride is S2C12.

6; A lubricating composition according to claim 4 wherein the sulfur chloride is 8612;

7. A lubricating composition consisting essentially of about by weight of mineral base lubricating oil, 7.5% of chlorinated wax, and 2.5% of a reaction product of a monocyclic terpene, treated first with about 1 to 2 mols per mol of said terpene of a sulfur chloride and treated thereafter with about 0.001 to 0.1 mols of a phosphorus sulfide at a temperature of to 175 C.

8. Composition according to claim 1 wherein the terpene is dipentene.

9. Composition according to claim 4 wherein the terpene is dipentene.

10. Composition according to claim 7 wherein the terpene is dipentene.

11. A method of preparing an extreme pressure additive for lubricants and the like, which consists in first reacting 1 molar proportion of a monocyclic terpene with about 1 to 2 molar proportions of sulfur chloride at a temperature between about 60 and C., the quantity of sulfur chloride being approximately that required to saturate one double bond of the terpene, and thereafter reacting the treated dipentene with about 0.001-to about 0.1 molar proportions of phosphorus sulfide at a temperature between about 125 and C. for a period of A to 2 hours to partially saturate a second double bond of said terpene.

12. A method of preparing a sulfur and phosphorus-containing organic compound which comprises treating a non-aromatic mono-cyclic terpenic C10 material having a six-membered unsaturated ring with approximately one to two molar equivalents of a sulfur chloride at a temperature of 60 to 125 C. for about to 2 hours, and subsequently treating the sulfur chloridetreated product with about 0.001 to 0.1 molar proportions of phosphorus sulfide at a temperature of 100 to C. for about to 2 hours.

13. Method according to claim 12 wherein the organic material is a terpene comprising a substantial proportion of dipentene.

14. Method according to claim 12 wherein the sulfur chloride is SC12.

15. Method according to claim 12 wherein the sulfur chloride is SzClz.

16. Method according to claim 12 wherein the phosphorus sulfide is P483.

17. The process which comprises treating a substantially mono-cyclic terpene composition comprising dipentene with 1 to 2 molar proportions, based on said terpene composition, of a sulfur chloride of one to two chlorine atoms persulfur atom at a temperature between 60 and 125 C. for to 2 hours and thereafter treating the reaction product with about 0.001 to 0.1 molar proportion of P4S3 at 125 to 150 C. for A, to 2 hours.

18. As a new composition of matter, the reaction product of a molar proportion of substantially mono-cyclic terpene composition containing a substantial proportion of dipentene treated first with about one to two mols of sulfur chloride having one to two chlorine atoms per sulfur atom The following references are of record in the REFERENCES CITED file of this patent:

5 UNITED STATES PATENTS Number Name Date 2,268,232 Whittier Dec. 30, 1941 2,307,183 Zimmer Jan. 5, 1943 2,413,648 Ott Dec. 31, 1946 10 2,468,520 Sproule Apr. 26, 1949 

1. AN EXTREME PRESSURE ADDITIVE COMPOSITION FOR LUBRICANTS CONSISTING ESSENTIALY OF THE REACTION PRODUCT OF ABOUT 1 MOLAR PROPORTION OF A MONOCYCLIC TERPENE WITH ABOUT 1 TO 2 MOLAR PROPORTIONS OF A SULFUR CHLORIDE, THE QUNTITY OF SAID SULFUR CHLORIDE BEING SUBSTANTIALLY SUFFICIENT TO SATURATE ONE DOUBLE BOND IN SAID TERPENE, SAID REACTION PRODUCT BEING FURTHER REACTED WITH ABOUT 0.001 TO 0.1 MOLAR PROPORTION OF PHOSPHORUS SULFIDE AT A TEMPERATURE OF 100* TO 175* C. 